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World Multidisciplinary Earth Sciences Symposium (WMESS 2019) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 362 (2019) 012096 doi:10.1088/1755-1315/362/1/012096

Coal Calorific Value after Physical and Chemical Cleaning

Serdar Yilmaz1, Ihsan Toroglu1, Dilek Cuhadaroglu1

1
Department of Mining Engineering, Zonguldak Bülent Ecevit University, 67100,
Zonguldak, Turkey

s_yilmaz67@hotmail.com

Abstract. In this study a total of 12 coal sample was collected. 7 of these samples are local coal
samples and 5 of them is exported coals. These coals samples were fractionated into two size
groups, i.e. -10+3.15, -3.15+05. Float and sink analysis was performed on this two size groups
of samples with Ca(NO3)2 medium at the density of 1.50 g/cm3. Latter within the scope of this
study, chemical cleaning was employed on this samples. Chemical cleaning on coal samples was
carried out with acids (HF and HNO3) at specific conditions. Samples have different calorific
values after physical and chemical cleaning. Although some impurities have been removed with
both cleaning methods, physical cleaning resulted in higher ash content coals at the end while
with chemical cleaning almost no ash content coals were obtained. However, it was observed the
fact that chemical cleaning resulted lower calorific values of samples. This might be because of
chemical cleaning results in the decomposition of the coal matrix structure.

1. Introduction
Coal is an organic material and it has some impurities within its structure. These impurities are
sometimes hard to remove away. In order to remove these mineral impurities, physical and chemical
cleaning methods are employed. Due to higher and higher energy requirements of the world and due to
the gradual depletion of high quality coal reserves, coal cleaning gains more importance day by day [1].
Mineral matter in coal have 3 forms; i. true minerals, ii. Dissolved salts in pore water, iii. Elements
associated with the hydrocarbonaceous matrix [2]. According to Sharma and Gihar [3], the major
minerals in coals are silicates or shales (kaolinite type), quartz and/or sandstone, pyrites and carbonates
such as siderites and ankerites.

Various treatments to remove mineral matter can be employed and these treatments result in different
mineral matter or ash content at the end [1]. Treatments or methods to remove the mineral matter can
be categorized into two main groups, i.e. physical and chemical cleaning. However both methods are
affected by the liberation of particles, in other words finer the size higher the rate of mineral matter
removal could be. Physical cleaning methods can reduce coal mineral impurities to some degree and it
can not lower further and that is why chemical cleaning has to be used to produce clean coal [4, 5]. In
terms of chemical cleaning, leaching with nitric acid [6], hydrofluoric acid [7], caustic soda in the
Gravimelt process [8], mixtures of hydrofluoric/hydrocloric acids [9], calcium hydroxide/hydrocloric
acid [10], sodium hydroxide/hydrocloric acid [11] and different acids [1] have been performed by
researchers [1, 6, 7, 8, 9, 10, 11]. Cleaned coal either with physical or chemical methods should be tested
in terms of its combustion behaviour [12,13,14,15] since there are some advantages and disadvantages
regarding these cleaning methods as such poor reactivity performance is attained [4].

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Published under licence by IOP Publishing Ltd 1
World Multidisciplinary Earth Sciences Symposium (WMESS 2019) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 362 (2019) 012096 doi:10.1088/1755-1315/362/1/012096

In this study collected coal samples were analysed in terms of their ash removal and calorific value
changes respectively before and after physical & chemical cleaning. Ash making mineral matters are
removed to some degree with physical cleaning and higher rate of removal was achieved with chemical
cleaning method. However, calorific values are higher after physical cleaning and lower after chemical
cleaning.

2. Experimental Method
In this study a total of 12 coal samples were collected and physical & chemical cleaning were employed.
The collected coal samples and their origins are tabulated in Table 1.

Table 1. Collected coal samples origins, locations and their corresponding codings.
Coal sample seam identity Origin of coal sample Corresponding coding
Çay TTK Karadon TB1
Büyük TTK Kozlu TB2
Azdavay Azdavay- Kastamonu TB3
Çınarlı TTK Amasra TB4
Büyük Damar TTK Armutçuk TB5
Sulu TTK Üzülmez TB6
Söğütözü Söğütözü-Kastamonu TB7
Goonyella Queensland-Avusturalya IT 1
Weglokoks Typr-R35 Silesia-Polonya IT 3
South Blackwater Blackwater-Avusturalya IT 4
Saraji Mackay-Queensland-Avusturalya IT 6
JWR-Bluecreek, No 7 Alabama-ABD IT 7

In this study, experimental work was carried out on local coal samples (TB1 to TB7) and exported
coal samples (IT1 to IT5). Local samples were taken from each coal seam as regards to TS 2942. A total
of 50-60 kg of coal was either collected from local coal seams or provided (exported). Schematical
representation of experimental procedure (physical cleaning) is provided in Figure 2.

After the process of physical cleaning, chemical cleaning with HF was employed. Chemical cleaning
with HF was realized in teflon beaker at various concentrations (1, 2, 3, 4, 5, 6 M). Coal sample (20 g)
was objected to 100 ml of acid (HF) solution (at 65 °C) for 3 hours and it was stirred with magnetic
stirrer. Latter, the solution was filtrated and filtrate was taken. The filtrate (chemically cleaned coal
sample) was dehumidified at 60 °C for 24 h. Corresponding concentration variation with respect to ash
removal is provided in Figure 1.

10

5
% Ash

0
0 1 2 3 4 5 6
Concentration of HF (M)

Figure 1. Concentration (HF) variation with respect to ash removal

2
World Multidisciplinary Earth Sciences Symposium (WMESS 2019) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 362 (2019) 012096 doi:10.1088/1755-1315/362/1/012096

Figure 2. Schematical representation experimental procedure for physical cleaning.

Referring back to Figure 1, chemical cleaning on all samples was performed with 3.5 M HF solution
since highest rate of ash reduction was observed between 3 M and 4 M solution

3. Results and discussions

The results of ash removal and calorific values after physical & chemical cleaning is provided in Table
2. Corresponding plot (Figure 3) of calorific value change with respect to ash removal is obtained.

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World Multidisciplinary Earth Sciences Symposium (WMESS 2019) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 362 (2019) 012096 doi:10.1088/1755-1315/362/1/012096

Table 2. Results of the ash content and calorific values after physical & chemical cleaning.
Sample After Physical Cleaning After Chemical Cleaning
Ash (%) Calorific Value Ash (%) Calorific Value
(kcal/kg) (kcal/kg)
TB1 8.63 7676 0.42 6776
TB2 9.68 7330 0.55 6476
TB3 8.73 7683 0.15 6157
TB4 7.71 6813 0.41 5686
TB5 4.32 7614 0.32 6597
TB6 7.57 7484 0.48 6723
TB7 8.13 7733 0.18 6406
IT 1 7.82 7908 0.07 6672
IT 3 6.64 7718 0.22 6952
IT 4 5.97 7800 0.19 6136
IT 6 8.36 7934 0.70 7169
IT 7 6.61 8067 0.67 7387

Referring to Table 2, ash content of each coal sample is between 4.32 and 9.68 % after physical
cleaning while it is between 0.07 and 0.70 % after chemical cleaning. Corresponding calorific values
are between 6813 and 8067 kcal/kg after physical cleaning while they are between 5686 and 7387
kcal/kg after chemical cleaning.

10 9000
9 8000

Calorific Value (kcal/kg)

8 7000
Ash Content (%)

7 6000
6
5000
5
4000
4
3 3000
2 2000
1 1000
0 0
TB1 TB2 TB3 TB4 TB5 TB6 TB7 IT1 IT3 IT4 IT6 IT7
Ash content after physical
8,63 9,68 8,73 7,71 4,32 7,57 8,13 7,82 6,64 5,97 8,36 6,61
cleaning
Ash content after chemical
0,42 0,55 0,15 0,41 0,32 0,48 0,18 0,07 0,22 0,19 0,7 0,67
Cleaning
Calorific values after physical
7676 7330 7683 6813 7614 7484 7733 7908 7718 7800 7934 8067
cleaning
Calorific Values after chemical
6776 6476 6157 5686 6597 6723 6406 6672 6952 6136 7169 7387
cleaning
Coal Sample

Ash content after physical cleaning Ash content after chemical Cleaning
Calorific values after physical cleaning Calorific Values after chemical cleaning

Figure 3. Graphical representation of ash content removal and corresponding calorific value change.

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World Multidisciplinary Earth Sciences Symposium (WMESS 2019) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 362 (2019) 012096 doi:10.1088/1755-1315/362/1/012096

As it can be observed from Figure 3, calorific values decreases after physical cleaning for all coal
samples studied. Referring back and forth to the Figure 3 and Table 2, 90-99 % of ash removal was
achieved after chemical cleaning. The lowest rate of ash removal (89.9 %) was observed on the sample
coded as IT7 and the highest ash removal percentage (99 %)is observed on IT1 sample. However after
chemical cleaning calorific values of coal samples decreased within the ratios between 8.4 and 21.3 %.
Highest ratio of calorific value decrease was observed on IT4 sample and the lowest one was observed
on IT7 sample. In order to tabulate these percentages of calorific value decreases and ash removal rates,
Table 3 is provided.

Table 3. Percentages of calorific value decreases and ash removal rates (%) after chemical cleaning.

Sample Ash removal Calorific value decrease rates

rates (%) (%)
TB1 95.13 11.72
TB2 94.32 11.65
TB3 98.28 19.86
TB4 94.68 16.54
TB5 92.59 13.36
TB6 93.66 10.17
TB7 97.79 17.16
IT 1 99.10 15.63
IT 3 96.69 9.92
IT 4 96.82 21.33
IT 6 91.63 9.64
IT 7 89.86 8.43

Table 3 is a good representation of each sample resistance to chemical cleaning. As it is mentioned

earlier some coal samples are better convenient for physical cleaning while some are convenient for
both cleaning methods. As it can be interfered from Table 3 that, IT4 sample can be regarded as not
convenient for chemical cleaning since it loses more than 20 % of its calorific value. However for IT7
sample, chemical cleaning resulted in the removal of almost 90 % of it ash content and its calorific value
decreased only 8 %. What can be summarized from these findings, some coal sample (IT7) favours
chemical cleaning while some (IT4) have decomposition of coal matrix with chemical cleaning.

As presented earlier, ultra clean coals or fuels have higher demands nowadays and in order to perform
this purpose, chemical cleaning is irreplaceable method. However some coals due to their structure and
mineral matter forms, chemical cleaning might or might not be convenient method to be employed.

4. Conclusions
In this study, coal ash content removal was employed with physical and chemical methods. Collected
coal samples (a total of 12, either local or exported) was physically cleaned in the first place. Right after
this physical cleaning their corresponding ash content and calorific values were determined. Secondly,
coal samples (physically cleaned) were objected to chemical cleaning at specified conditions. Chemical
cleaning resulted in higher rates of ash removal while it resulted in significant decreases in calorific
values. Chemical cleaning not necessarily always but most of the time results in decomposed coal matrix
and a decrease in calorific value is understandable. However, for some specific coal samples studied
have significant amount of calorific value decrease while other samples have respectively 2-3 times
lower ratios of this decrease. It was concluded that, some samples are more convenient in terms of
chemical cleaning while others have more tendency to have the decomposed coal matrix at the end. In

5
World Multidisciplinary Earth Sciences Symposium (WMESS 2019) IOP Publishing
IOP Conf. Series: Earth and Environmental Science 362 (2019) 012096 doi:10.1088/1755-1315/362/1/012096

the order of clean coal production, one should take the findings of this study into account as regards to
chemical cleaning. Before chemical cleaning, one should characterize the coal sample tendency or
resistance to chemical cleaning, and this study could be beneficial as regards to this characterization.
What was concluded in this study is, out of these 12 samples, IT4 sample can be considered as not
convenient for chemical cleaning while IT7 sample is rather convenient. A classification method
(convenient, inconvenient) should be further proposed within the future scope of this study.

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